Polymerization catalyst, production and use

ABSTRACT

Ethylene and alpha-olefins are homopolymerized or copolymerized with another olefin monomer in the presence of a catalyst system comprising an organo metal cocatalyst and a titanium containing catalyst component, said titanium-containing catalyst component being obtained by reacting together a porous particulate material, an organic magnesium compound, an oxygen containing compound, an acyl halide and titanium tetrachloride and a Group IIIa hydrocarbyl metal dihalide.

This is a division of application Ser. No. 638,168 filed 08/06/84 andnow U.S. Pat. No. 4,558,025.

BACKGROUND OF THE INVENTION

This invention relates to a novel catalyst component to be employed witha cocatalyst for use in the polymerization of olefins to polyolefinssuch as polyethylene, polypropylene and the like and especially in theproduction of high density and linear low density polyethylene,copolymers such as ethylene copolymers with other alpha-olefins anddiolefins, which catalyst component shows unusually high activity andexcellent hydrogen response for the control of polymer molecular weightwhile obtaining improved comonomer response and improved bulk density.The polymer product obtained evidences an important balance of polymerproperties, for example, the catalyst system obtains a polymer with goodbulk density, a narrow molecular weight distribution and an improvedbalance in polymer product machine direction tear strength andtransverse direction tear strength. As a result, for example, the blownfilm produced from LLDPE manifests an overall high strength.

The catalyst component comprises a solid reaction product obtained bycontacting a solid, particulate, porous support material such as, forexample, silica, alumina, magnesia or mixtures thereof, for example,silica-alumina, in stages with a transition metal compound, anorganometallic composition treated with an alcohol, an acyl halide and aGroup IIIa metal hydrocarbyl dihalide. The novel catalyst component,which when used with an aluminum alkyl cocatalyst, provides the novelcatalyst system of this invention which can be usefully employed for thepolymerization of olefins.

The catalyst system can be employed in slurry, single-phase melt,solution and gas-phase polymerization processes and is particularlyeffective for the production of linear polyethylenes such as highdensity polyethylene and linear low density polyethylene.

Recently, interest has arisen in the use of magnesium-titanium complexcatalyst components for the polymerization of olefins. For example,European Patent Application No. 27733, published Apr. 29, 1981 disclosesa catalyst component obtained by reducing a transition metal compoundwith an excess of organomagnesium compound in the presence of a supportsuch as silica and thereafter deactivating the excess organomagnesiumcompound with certain deactivators including hydrogen chloride.

U.S. Pat. No. 4,136,058 discloses a catalyst component comprising anorganomagnesium compound and a transition metal halide compound, whichcatalyst component is thereafter deactivated with a deactivating agentsuch as hydrogen chloride. This patent des not teach the use of supportmaterial such as silica but otherwise the disclosure is similar to theabove-discussed European patent application.

U.S. Pat. No. 4,250,288 discloses a catalyst which is the reactionproduct of a transition metal compound, an organomagnesium component andan active non-metallic halide such as HCl and organic halides containinga labile halogen. The catalyst reaction product also contains somealuminum alkyls.

Catalyst components comprising the reaction product of an aluminumalkyl-magnesium alkyl complex plus titanium halide are disclosed in U.S.Pat. No. 4,004,071 and U.S. Pat. No. 4,276,191.

U.S. Pat. Nos. 4,173,547 and 4,263,171, respectively disclose a catalystcomponent comprising silica, an organoaluminum compound, titaniumtetrachloride and dibutyl magnesium and a catalyst component comprisinga magnesium alkyl-aluminum alkyl complex plus titanium halide on asilica support.

Each of U.S. Pat. Nos. 4,402,861, 4,378,304, 4,388,220, 4,301,029 and4,385,161 disclose supported catalyst systems comprising an oxidesupport such as silica, an organomagnesium compound, a transition metalcompound and one or more catalyst component modifiers. These patents donot disclose the catalysts of this invention.

In British No. 2,101,610 silica is treated with a magnesium alkyl, analcohol, benzoyl chloride and TiCl₄. In each of Japanese Kokai No.50-098206 and 57-070107 acyl halides are employed during the preparationof titanium supported catalysts.

The catalyst systems comprising magnesium alkyls and titanium compounds,although useful for the polymerization of olefins such as ethylene andother 1-olefins, often do not show excellent responsiveness to hydrogenduring the polymerization reaction for the control of molecular weight,do not readily incorporate comonomers such as butene-1 for theproduction of ethylene copolymers, do not show an extremely highcatalytic activity and obtain polymer product manifesting poor bulkdensity and film properties which are unbalanced under anisotropicconditions.

In U.S. Pat. No. 4,451,574 issued May 29, 1984 a catalyst systemobtained by treating an inert particulate support, such as silica, withan organometallic compound, a titanium halide and a halogen gas isdisclosed. Although the catalyst obtains very high activities, there isa need for improving the film properties of polymer product obtained bypolymerizing olefins in the presence of the catalyst and to improve thebulk density of polymer product.

In accordance with this invention catalyst combinations have been foundwhich have extremely high catalytic activities and excellent hydrogenresponsiveness for the control of molecular weight and obtain polymerproduct with greatly improved film properties and bulk density. Theresins exhibit excellent melt strength with a surprising decrease inpower consumption hence an increase in extrusion rates, as well asexcellent MD tear strength in excess of 80 g/mil and dart impactstrength in excess of 70 g/mil with a 1.0 dg/min and 0.918 g/cc densityfilm.

The new catalyst systems and catalyst component of this invention areobtained by contacting an organometallic compound, an alcohol, an acylhalide, a transition metal compound and a Group IIIa metal hydrocarbyldihalide in the presence of a oxide support. The catalyst systememploying the transition metal containing catalyst component isadvantageously employed in a gas phase ethylene polymerization processsince there is a significant decrease in reactor fouling as generallycompared with catalytic prior art ethylene gas phase polymerizationprocesses thereby resulting in less frequent reactor shut downs forcleaning.

SUMMARY OF THE INVENTION

In accordance with the objectives of this invention there is provided atransition metal containing catalyst component for the polymerization ofalpha-olefins comprising a solid reaction product obtained by treatingan inert solid support material in an inert solvent sequentially with(A) an organometallic compound of a Group IIa, IIb or IIIa metal of thePeriodic Table wherein all the metal valencies are satisfied with ahydrocarbon or substituted hydrocarbon group, (B) an oxygen containingcompound selected from ketones, aldehydes, alcohols, siloxanes ormixtures thereof, (C) an acyl halide, (D) at least one transition metalcompound of a Group IVb, Vb, VIb, or VIII metal of the Periodic Table,and (E) a Group IIIa metal hydrocarbyl dihalide with the proviso thatthe inert solid support material can alternatively be treated with (i)the (A) organometallic compound and the (B) oxygen containing compoundsimultaneously, (ii) the reaction product of the (A) organometalliccompound and (B) oxygen containing compound or (iii) the (B) oxygencontaining compound followed by treating with the (A) organometalliccompound.

The solid transition metal containing catalyst component when employedin combination with a cocatalyst such as an alkyl aluminum cocatalystprovides a catalyst system which demonstrates a number of uniqueproperties that are of great importance in the olefin polymerizationtechnology such as, for example, extremely high catalytic activity, theability to control the molecular weight during the polymerizationreaction as a result of the improved responsiveness to hydrogen,increased polymer yield, and especially improved comonomer response andreduced reactor fouling. The polymer product obtained from thepolymerization of olefins and particularly ethylene manifests improvedbulk density, melt strength and tear strength.

In a preferred embodiment of the invention the (A) organometalliccompound is a dihydrocarbon magnesium compound represented by R¹ MgR²wherein R¹ and R² which can be the same or different are selected fromalkyl groups, aryl groups, cycloalkyl groups, aralkyl groups, alkadienylgroups or alkenyl groups having from 1 to 20 carbon atoms, the (B)oxygen containing compounds are selected from alcohols and ketonesrepresented by the formula R³ OH and R⁴ COR⁵ wherein R³ and each of R⁴and R⁵ which may be the same or different can be an alkyl group, arylgroup, cycloalkyl group, aralkyl group, alkadienyl group or alkenylgroup having from 1 to 20 carbon atoms, the (D) transition metalcompound is preferably a transition metal compound or combination oftransition metal compounds represented by the formulas TrX'_(4-q)(OR⁶)_(q), TrX'_(4-q) R_(q) ⁷, VO(OR⁶)₃ and VOX'₃ wherein Tr is atransition metal of Groups IVb, Vb, VIb, VIIb and VIII and preferablytitanium, vanadium or zirconium, R⁶ is an alkyl group, aryl group,aralkyl group, substituted aralkyl group having from 1 to 20 carbonatoms and 1,3-cyclopentadienyls, X' is halogen and q is zero or a numberless than or equal to 4, and R⁷ is an alkyl group, aryl group or aralkylgroup having from 1-20 carbon atoms or a 1,3-cyclopentadienyl. In aparticularly preferred embodiment of the invention the (A)organometallic compound and the (B) oxygen containing compound arereacted together prior to contact with the inert support.

All references to the Periodic Table are to the Periodic Table of theElements printed on page B-3 of the 56th Edition of Handbook ofChemistry and Physics, CRC Press (1975).

In a second embodiment of this invention there is provided a catalystsystem comprising the transition metal containing solid catalystcomponent and an organoaluminum cocatalyst for the polymerization ofalpha-olefins using the catalyst of this invention under conditionscharacteristic of Ziegler polymerization.

In view of the high activity of the catalyst system prepared inaccordance with this invention as compared with conventional Zieglercatalysts, it is generally not necessary to deash polymer product sincepolymer product will generally contain lower amounts of catalystresidues than polymer product produced in the presence of conventionalcatalyst.

The catalyst systems can be employed in a gas phase process, singlephase melt process, solvent process or slurry process. The catalystsystem is usefully employed in the polymerization of ethylene and otheralpha-olefins, particularly alpha-olefins having from 3 to 8 carbonatoms and copolymerization of these with other 1-olefins or diolefinshaving from 2 to 20 carbon atoms, such as propylene, butene, pentene andhexene, butadiene, 1,4-pentadiene and the like so as to form copolymersof low and medium densities. The supported catalyst system isparticularly useful for the polymerization of ethylene andcopolymerization of ethylene with other alpha-olefins in gas phaseprocesses.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Briefly, the catalyst components of the present invention comprises thesolid reaction product of (A) an organometallic compound, (B) an oxygencontaining compound, (C) an acyl halide, (D) at least one transitionmetal compound and (E) a Group IIIa metal hydrocarbyl dihalide in thepresence of an oxide support material. According to the polymerizationprocess of this invention, ethylene, at least one alpha-olefin having 3or more carbon atoms or ethylene and other olefins or diolefins havingterminal unsaturation are contacted with the catalyst under polymerizingconditions to form a commercially useful polymeric product. Typically,the support can be any of the solid particulate porous supports such astalc, zirconia, thoria, magnesia, and titania. Preferably the supportmaterial is a Group IIa, IIIa, IVa and IVb metal oxide in finely dividedform.

Suitable inorganic oxide materials which are desirably employed inaccordance with this invention include silica, alumina, andsilica-alumina and mixtures thereof. Other inorganic oxides that may beemployed either alone or in combination with the silica, alumina orsilica-alumina are magnesia, titania, zirconia, and the like. Othersuitable support materials, however, can be employed. For example,finely divided polyolefins such as finely divided polyethylene.

The metal oxides generally contain acidic surface hydroxyl groups whichwill react with the organometallic composition or transition metalcompound first added to the reaction solvent. Prior to use, theinorganic oxide support is dehydrated, i.e., subject to a thermaltreatment in order to remove water and reduce the concentration of thesurface hydroxyl groups. The treatment is carried out in vacuum or whilepurging with a dry inert gas such as nitrogen at a temperature of about100° to about 1000° C., and preferably from about 300° C. to about 800°C. Pressure considerations are not critical. The duration of the thermaltreatment can be from about 1 to about 24 hours. However, shorter orlonger times can be employed provided equilibrium is established withthe surface hydroxyl groups.

Chemical dehydration as an alternative method of dehydration of themetal oxide support material can advantageously be employed. Chemicaldehydration converts all water and hydroxyl groups on the oxide surfaceto inert species. Useful chemical agents are, for example, SiCl₄,chlorosilanes, silylamines and the like. The chemical dehydration isaccomplished by slurrying the inorganic particulate material, such as,for example, silica in an inert low boiling hydrocarbon, such as, forexample, heptane. During the chemical dehydration reaction, the silicashould be maintained in a moisture and oxygen-free atmosphere. To thesilica slurry is then added a low boiling inert hydrocarbon solution ofthe chemical dehydrating agent, such as, for example,dichlorodimethylsilane. The solution is added slowly to the slurry. Thetemperature ranges during chemical dehydration reaction can be fromabout 25° C. to about 120° C., however, higher and lower temperaturescan be employed. Preferably the temperature will be about 50° C. toabout 70° C. The chemical dehydration procedure should be allowed toproceed until all the moisture is removed from the particulate supportmaterial, as indicated by cessation of gas evolution. Normally, thechemical dehydration reaction will be allowed to proceed from about 30minutes to about 16 hours, preferably 1 to 5 hours. Upon completion ofthe chemical dehydration, the solid particulate material is filteredunder a nitrogen atmosphere and washed one or more times with a dry,oxygen-free inert hydrocarbon solvent. The wash solvents, as well as thediluents employed to form the slurry and the solution of chemicaldehydrating agent, can be any suitable inert hydrocarbon. Illustrativeof such hydrocarbons are heptane, hexane, toluene, isopentane and thelike.

The preferred (A) organometallic compounds employed in this inventionare the inert hydrocarbon soluble organomagnesium compounds representedby the formula R¹ MgR² wherein each or R¹ and R² which may be the sameor different are alkyl groups, aryl groups, cycloalkyl groups, aralkylgroups, alkadienyl groups or alkenyl groups. The hydrocarbon groups R¹or R² can contain between 1 and 20 carbon atoms and preferably from 1 toabout 10 carbon atoms. Illustrative but non-limiting examples ofmagnesium compounds which may be suitably employed in accordance withthe invention are dialkylmagnesiums such as diethylmagnesium,dipropylmagnesium, di-isopropylmagnesium, di-n-butylmagnesium,di-isobutylmagnesium, diamylmagnesium, dioctylmagnesium,di-n-hexylmagnesium, didecylmagnesium, and didodecylmagnesium;dicycloalkylmagnesium, such as dicyclohexylmagnesium; diarylmagnesiumsuch as dibenzylmagnesium, ditiolylmagnesium and dixylylmagnesium.

Preferably the organomagnesium compounds will have from 1 to 6 carbonatoms and most preferably R¹ and R² are different. Illustrative examplesare ethylpropylmagnesium, ethyl-n-butylmagnesium, amylhexylmagnesium,n-butyl-s-butylmagnesium, and the like. Mixtures of hydrocarbylmagnesium compounds may be suitably employed such as for example dibutylmagnesium and ethyl-n-butyl magnesium.

The magnesium hydrocarbyl compounds are as generally obtained fromcommercial sources as mixtures of the magnesium hydrocarbon compoundswith a minor amount of an aluminum hydrocarbyl compound. The minoramount of aluminum hydrocarbyl is present in order to facilitatesolubilization of the organomagnesium compound in a hydrocarbon solvent.The hydrocarbon solvent usefully employed for the organomagnesium can beany of the well known hydrocarbon liquids, for example hexane, heptane,octane, decane, dodecane, or mixtures thereof as well as aromatichydrocarbons such as benzene, toluene, xylenes, etc.

The organomagnesium complex with a minor amount of aluminum alkyl can berepresented by the formula (R¹ MgR²)_(p) (R_(n) ⁸ Al)_(s) wherein R¹ andR² are defined as above and R⁸ has the same definition, n is an integerfrom 1 to 3, p is greater than 0, and the ratio of s/s+p is from 0 to 1,preferably from 0 to about 0.7 and most desirably from about 0 to 0.1.

Illustrative examples of the magnesium aluminum complexes are [(n-C₄H₉)(C₂ H₅)Mg][(C₂ H₅)₃ Al]₀.02,[(nC₄ H₉)₂ Mg][(C₂ H₅)₃ Al]₀.013, [nC₄H₉)₂ Mg][(C₂ H₅)₃ Al]₂.0 and [(nC₆ H₁₃)₂ Mg][(C₂ H₅)₃ Al]₀.01. Asuitable magnesium aluminum complex is Magala® BEM manufactured by TexasAlkyls, Inc.

The hydrocarbon soluble organometallic compositions are known materialsand can be prepared by conventional methods. One such method involves,for example, the addition of an appropriate aluminum alkyl to a soliddialkyl magnesium in the presence of an inert hydrocarbon solvent. Theorganomagnesium-organoaluminum complexes are, for example, described inU.S. Pat. Nos. 3,737,393 and 4,004,071 which are incorporated herein byreference. However, any other suitable method for preparation oforganometallic compounds can be suitably employed.

The oxygen containing compounds which may be usefully employed inaccordance with this invention are alcohols, aldehydes, siloxanes andketones. Preferably the oxygen containing compounds are selected fromalcohols and ketones represented by the formulas R³ OH and R⁴ COR⁵wherein R³ and each or R⁴ and R⁵ which may be the same or different canbe alkyl groups, aryl groups, cycloalkyl groups, aralkyl groups,alkadienyl groups, or alkenyl groups having from 2 to 20 carbon atoms.Preferably the R groups will have from 2 to 10 carbon atoms. Mostpreferably the R groups are alkyl groups and will have from 2 to 6carbon atoms. Illustrative examples of alcohols which may be usefullyemployed in accordance with this invention are ethanol, isopropanol,1-butanol, t-butanol, 2-methyl-1-pentanol, 1-pentanol, 1-dodecacanol,cyclobutanol, benzyl alcohol, and the like; diols, such as1,6-hexanediol, and the like with the proviso that the dial be contactedwith the magnesium compound subsequent to the magnesium compoundtreatment of the support material. Most preferably the alcohol willcontain from 1 to 4 carbon atoms. The most preferred alcohol is1-butanol.

The ketones will preferably have from 3 to 11 carbon atoms. Illustrativeketones are methyl ketone, ethyl ketone, propyl ketone, n-butyl ketoneand the like. Acetone is the ketone of choice.

Illustrative of the aldehydes which may be usefully employed in thepreparation of the organomagnesium compound include formaldehyde,acetaldehyde, propionaldehyde, butanal, pentanal, hexanal, heptanal,octanal, 2-methylpropanal, 3-methylbutanal, acrolein, crotonaldehyde,benzaldehyde, phenylacetaldehyde, o-tolualdehyde, m-tolualdehyde, andp-tolualdehyde.

Illustrative of the siloxanes which may be usefully employed in thepreparation of the organomagnesium compound includehexamethyldisiloxane, octamethyltrisiloxane,octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,sym-dihydrotetramethyldisiloxane, pentamethyltrihydrotrisiloxane,methylhydrocyclotetrasiloxane, both linear and branchedpolydimethylsiloxanes, polymethylhydrosiloxanes,polyethylhydrosiloxanes, polymethylethylsiloxanes,polymethyloctylsiloxanes, and polyphenylhydrosiloxanes.

Any of the acyl halides may be usefully employed in accordance with thisinvention. The hydrocarbon portion of the acyl halides which can havefrom 1-20 carbon atoms can be an alkyl group, substituted alkyl group,aryl group, substituted aryl group, cycloalkyl group, alkadienyl groupor alkenyl group.

The preferred acyl halides can be represented by the formula R⁹ COXwherein R⁹ can be C₁ to C₂₀ alkyl group, substituted alkyl group, arylgroup, substituted aryl group, or cycloalkyl group and X is a halogen.The preferred halogen is chlorine.

Illustrative but non-limiting examples of the acyl halides which can beemployed in this invention are acetyl chloride, propanoyl chloride,butyryl chloride, butyryl bromide, isobutyryl chloride, benzoylchloride, oleoyl chloride, acryloyl chloride, 6-hepteneoyl chloride,heptanoyl chloride, cyclohexanecarbonyl chloride, cyclopentanepropionylchloride and the like. Acid chlorides based on polyacids may alsousefully be employed such as, for example, dodecanedioyl chloride,succinyl chloride, camphoryl chloride, terephthalloyl chloride and thelike. The preferred acid halides are acetyl chloride, benzoyl chloride,and p-methylbenzoyl chloride.

The transition metal compounds of a Group IVa, Va, VIa or a metal whichcan be usefully employed in the preparation of the transition metalcontaining catalyst component of this invention are well known in theart. The transition metals which can be employed in accordance with thisinvention may be represented by the formulas TrX'_(4-q) (OR⁶)_(q),TrX'_(4-q) R_(q) ⁷, VOX'₃ and VO(OR⁶)₃. Tr is a Group IVb, Vb, VIb,VIIb, and VIII metal, preferably Group IVb and Vb metals and preferablytitanium, vanadium or zirconium, q is 0 or a number equal to or lessthan 4, X' is halogen, R⁶ is a hydrocarbyl or substituted hydrocarbylgroup, for example, alkyl, aryl or cycloalkyl having from 1 to 20 carbonatoms and R⁷ is an alkyl group, aryl group, aralkyl group, substitutedaralkyl group, 1,3-cyclopentadienyls and the like. The alkyl, aryl,aralkyls and substituted aralkyls contain from 1 to 20 carbon atomspreferably 1 to 10 carbon atoms. Mixtures of the transition metalcompounds can be employed if desired.

Illustrative examples of the transition metal compounds include: TiCl₄,TiBr₄, Ti(OCH₃)₃ Cl, Ti(OC₂ H₅)Cl₃, Ti(OC₄ H₉)₃ Cl, Ti(OC₃ H₇)₂ Cl₂,Ti(OC₆ H₁₃)₂ Cl₂, Ti(OC₈ H₁₇)₂ Br₂, and Ti(OC₁₂ H₂₅)Cl₃.

As indicated above, mixtures of the transition metal compounds may beusefully employed, no restriction being imposed on the number oftransition metal compounds which may be reacted with the organometalliccomposition. Any halogenide and alkoxide transition metal compound ormixtures thereof can be usefully employed. The titanium tetrahalides areespecially preferred with titanium tetrachloride being most preferred.

The Group III hydrocarbyl dihalides are at least employed in the laststep of the transition metal containing catalyst component. Preferablythe Group III metal hydrocarbyl dihalides are selected from the boronand aluminum alkyl dihalides. The alkyl group can have from 1 to 12carbon atoms.

Illustrative, but non-limiting examples of the Group III metal alkylhalides are methyl aluminum dichloride, ethyl aluminum dichloride,propyl aluminum dichloride, butyl aluminum dichloride, isobutyl aluminumdichloride, pentyl aluminum dichloride, neopentyl aluminum dichloride,hexyl aluminum dichloride, octyl aluminum dichloride, decyl aluminumdichloride, dodecyl aluminum dichloride, methyl boron dichloride, ethylboron dichloride, propyl boron dichloride, butyl boron dichloride,isobutyl boron dichloride, pentyl boron dichloride, neopentyl borondichloride, hexyl boron dichloride, octyl boron dichloride, decyl borondichloride and the like. The preferred Group III metal alkyl dihalidesare ethyl aluminum dichloride and ethyl boron dichloride. Preferably,the treatment with the Group III metal alkyl dihalides will be fromabout 4 hours to 16 hours, however, greater or lesser time can be usedfor the treatment.

The treatment of the support material as mentioned above is conducted inan inert solvent. The inert solvents can also be usefully employed todissolve the individual ingredients prior to the treatment step.Preferred solvents include mineral oils and the various hydrocarbonswhich are liquid at reaction temperatures and in which the individualingredients are soluble. Illustrative examples of useful solventsinclude the alkanes such as pentane, iso-pentane, hexane, heptane,octane and nonane; cycloalkanes such as cyclopentane, cyclohexane; andaromatics such as benzene, toluene, ethylbenzene and diethylbenzene. Theamount of solvent to be employed is not critical. Nevertheless, theamount should be employed so as to provide adequate heat transfer awayfrom the catalyst components during reaction and to permit good mixing.

The organometallic component employed in step (A) either as theorganometallic compound or its reaction product with the oxygencontaining compound is preferably added to the inert solvent in the formof a solution. Preferred solvents for the organometallic compositionsare the alkanes such as hexane, heptane, octane and the like. However,the same solvent as employed for the inert particulate support materialcan be employed for dissolving the organometallic composition. Theconcentration of the organometallic composition in the solvent is notcritical and is limited only by handling needs.

The amounts of materials usefully employed in the solid catalystcomponent can vary over a wide range. The concentration of magnesiumdeposited on the essentially dry, inert support can be in the range fromabout 0.1 to about 2.5 millimoles/g of support, however, greater orlesser amounts can be usefully employed. Preferably, the organomagnesium compound concentration is in the range of 0.5 to 2.0millimoles/g of support and more preferably in the range of 1.0 to 1.8millimoles/g of support. The magnesium to oxygen-containing compoundmole ratio can range from about 0.01 to about 2.0. Preferably, the ratiois in the range 0.5 to 1.5, and more preferably in the range 0.8 to 1.2.The upper limit on this range is dependent on the choice ofoxygen-containing compound and the mode of addition. When theoxygen-containing compound is not premixed with the magnesium compound,that is, when it is added to the support before the magnesium compoundor after the magnesium compound, the ratio may range from 0.01 to 2.0.When premixed with the organomagnesium compound, the hydrocarbyl groupson the oxygen-containing compound must be sufficiently large to insuresolubility of the reaction product. Otherwise the ratio ofoxygen-containing compound to organomagnesium compound ranges from 0.01to 1.0, most preferably 0.8 to 1.0. The amount of acyl halide employedshould be such as to provide a mole ratio of about 0.1 to about 10 andpreferably 0.5 to about 2.5 with respect to the magnesium compound.Preferably the mole ratio will be from about 1 to about 2.

The Group IIIa metal hydrocarbyl dihalide employed can be in the rangeof about 0.1 to about 10 mmoles per mole of magnesium compound with apreferred range of from 0.5 to 5.0. The transition metal compound isadded to the inert support at a concentration of about 0.01 to about 1.5millimoles Ti/g of dried support, preferably in the range of about 0.05to about 1.0 millimoles Ti/g of dried support and especially in therange of about 0.1 to 0.8 millimoles Ti/g of dried support.

Generally, the individual reaction steps can be conducted astemperatures in the range of about -50° C. to about 150° C. Preferredtemperature ranges are from about -30° C. to about 60° C. with -10° C.to about 50° C. being most preferred. The reaction time for theindividual treatment steps can range from about 5 minutes to about 24hours. However, lesser or greater times can be employed. Preferably thereaction time will be from about 1/2 hour to about 8 hours. During thereaction constant agitation is desirable.

In the preparation of the titanium containing catalyst component washingafter the completion of any step may be effected. However, it isgenerally found that the advantages of the catalyst system arediminished by washing until the last step. The catalyst componentprepared in accordance with this invention are usefully employed withthe cocatalyst well known in the art of the Ziegler catalysis forpolymerization of olefins.

Typically, the cocatalysts which are used together with the transitionmetal containing catalyst component are organometallic compounds ofGroup Ia, IIa, IIIa metals such as aluminum alkyls, aluminum alkylhydrides, lithium aluminum alkyls, zinc alkyls, magnesium alkyls and thelike. The cocatalysts desirably used are the organoaluminum compounds.The preferred alkylaluminum compounds are represented by the formulaAlR"'_(n) X"_(3-n) wherein R"' is hydrogen, hydrocarbyl or substitutedhydrocarbyl group and X" is halogen. Preferably R"' is an alkyl grouphaving from 2 to 8 carbon atoms. Illustrative examples of the cocatalystmaterial are ethyl aluminum dichloride, ethyl aluminum sesquichloride,diethyl aluminum chloride, aluminum triethyl, aluminum tributyl,diisobutyl aluminum hydride, diethyl aluminum ethoxide and the like.Aluminum trialkyl compounds are most preferred with triisobutylaluminumbeing highly desirable.

The catalyst system comprising the aluminum alkyl cocatalyst and thetransition metal containing catalyst component is usefully employed forthe polymerization of ethylene, other alpha-olefins having from 3 to 20carbon atoms, such as for example, propylene, butene-1, pentene-1,hexene-1, 4 methylpentene-1, and the like and ethylene copolymers withother alpha-olefins or diolefins such as 1,4-pentadiene, 1,5-hexadiene,butadiene, 2-methyl-1,3-butadiene and the like. The polymerizablemonomer of preference is ethylene. The catalyst may be usefully employedto produce polyethylene or copolymers of ethylene by copolymerizing withother alpha-olefins or diolefins, particularly propylene, butene-1,pentene-1, hexene-1, and octene-1. The olefins can be polymerized in thepresence of the catalysts of this invention by any suitable knownprocess such as, for example, suspension, solution and gas-phasepolymerization processes.

The polymerization reaction employing catalytic amounts of theabove-described catalyst can be carried out under conditions well knownin the art of Ziegler polymerization, for example, in an inert diluentat a temperature in the range of 50° C. to 100° C. and a pressure of 2and 40 atmospheres, in the gas phase at a temperature range of 70° C. to100° C. at about 5 atmospheres and upward. Illustrative of the gas-phaseprocesses are those disclosed in U.S. Pat. No. 4,302,565 and U.S. Pat.No. 3,302,566 which references are incorporated by reference. Asindicated above, one advantageous property of the catalyst system ofthis invention is the reduced amount of gas phase reactor fouling. Thecatalyst system can also be used to polymerize olefins at single phaseconditions, i.e., 150° C. to 320° C. and 1,000-3,000 atmospheres. Atthese conditions the catalyst lifetime is short but the activitysufficiently high that removal of catalyst residues from the polymer isunnecessary. However, it is preferred that the polymerization be done atpressures ranging from 1 to 50 atmospheres, preferably 5 to 25atmospheres.

In the processes according to this invention it has been discovered thatthe catalyst system is highly responsive to hydrogen for the control ofmolecular weight. Other well known molecular weight controlling agentsand modifying agents, however, may be usefully employed.

The polyolefins prepared in accordance with this invention can beextruded, mechanically melted, cast or molded as desired. They can beused for plates, sheets, films and a variety of other objects.

While the invention is described in connection with the specificexamples below, it is understood that these are only for illustrativepurposes. Many alternatives, modifications and variations will beapparent to those skilled in the art in light of the below examples andsuch alternatives, modifications and variations fall within the generalscope of the claims.

In the Examples following the silica support was prepared by placingDavison Chemical Company G-952 silica gel in a vertical column andfluidizing with an upward flow of N₂.The column was heated slowly to600° C. and held at that temperature for 12 hours after which the silicawas cooled to ambient temperature.

The melt index (MI) and melt index ratio were measured in accordancewith ASTM test D1238. The resin density was determined by densitygradient column according to ASTM test D1505. The bulk density wasdetermined by allowing approximately 120 cc of resin to fall from thebottom of a polyethylene funnel across a gap of 1 inch into a tared 100cc plastic cylinder (2.6 cm in diameter by 19.0 cm high). The funnelbottom was covered with a piece of cardboard until the funnel was filledwith the sample. The entire sample was then allowed to fall into thecylinder. Without agitating the sample, excess resin was scraped away sothat the container was completely filled without excess. The weight ofresin in the 100 cc cylinder was determined. This measurement wasrepeated three times and the average value reported.

EXAMPLE 1 Catalyst Preparation

Into a vial containing 20 ml of hexane there was injected 10 ml ofbutylethylmagnesium (BEM) (6.8 mmoles Mg) to the solution was added 0.5ml (6.8 mmoles) of n-butanol. The mixture was allowed to react at roomtemperature for 1.5 hours. The solution was added to a vial containing3.5 g of the Davison 952 silica and reacted with the silica for 1 hourat room temperature. To the reaction mixture was added with stirring 6.8mmoles of benzoyl chloride. The reaction mixture was stirred at roomtemperature for 1 hour. To the slurry there was added 2.3 mmoles TiCl₄and the treatment was continued for 1 hour. Ethyl aluminum dichloride(15.7 mmoles Al) was added and the reaction continued for 1 hour. Thecatalyst turned light brown. The catalyst was filtered, washed 3 timeswith hexane and dried in vacuo.

Polymerization

To a 1.8 liter reactor there was added 800 cc of hexane, 0.10 g of thetitanium containing solid catalyst component, triisobutyl aluminumcocatalyst in an amount so as to provide an aluminum to titanium ratioof 50 mmoles. The vessel was pressured to 30 psig with H₂, 45 cc of1-butene was added and the vessel was thereafter pressured to 150 psigwith ethylene. The vessel was heated to 85° C. and polymerization wasmaintained for 40 minutes. The results of the polymerization aresummarized in Table 1.

EXAMPLE 2

The titanium containing product was prepared identically as in Example 1with the exception that octanol was used in place of butanol. Thepolymerization conditions were identical to that in Example 1. Theresults are of the polymerization are summarized in Table 1.

EXAMPLE 3

The titanium containing solid was prepared identically as in Example 1with the exception that acetyl chloride was used in place of benzoylchloride. The polymerization was performed as in Example 1. The resultsare summarized in Table 1.

EXAMPLE 4

The titanium containing solid product was prepared identically as inExample 1 with the exception that the ethyl aluminum dichloride reactionwas maintained for 16 hours and the polymerization conditions were as inExample 1 with the exception that 1-butene was omitted andpolymerization time was maintained for 90 minutes. The results of thepolymerization are summarized in Table 1.

EXAMPLE 5

The titanium containing solid product was prepared identically as inExample 4. The polymerization was as in Example 4 with the exceptionthat the polymerization time was maintained for 40 minutes.

EXAMPLE 6

The titanium containing solid catalyst component was preparedidentically as in Example 1 with the ethyl aluminum dichloride reactiontime maintained for 1 hour. The polymerization was performed as inExample 4. The results of the polymerization are summarized in Table 1.

COMPARATIVE EXAMPLE 1

The catalyst was prepared identically as in Example 1 with the exceptionthat BEM was added directly to the silica in the absence of any butanolor acyl halide addition. The polymerization was performed as inExample 1. The results of the polymerization are summarized in Table 1.

COMPARATIVE EXAMPLE 2

The titanium containing solid catalyst component was preparedidentically as in Example 1 with the exception that the EADC ? ? ? ?treatment was omitted. The polymerization was performed as in Example 1.The results of the polymerization are summarized in Table 1.

                                      TABLE I                                     __________________________________________________________________________                                 Specific Activity      Polymer                                                                             Bulk                                             (Kg PE/g  MI    MIR    Density                                                                             Density             Formulation                  Ti-hr-atm)                                                                              (g/10 min)                                                                          (HLMI/MI)                                                                            (g/ml)                                                                              (lb/ft.sub.3)       __________________________________________________________________________    (1) Silica + (BEM + BuOH) + BzCl + TiCl.sub.4 + EADC                                                       50.2      4.40  26.7   0.9322                                                                              --                  (2) Silica + (BEM + Octanol) + BzCl + TiCl.sub.4 + EADC                                                    79.2      10.2  26.7   0.9244                                                                              chunks              (3) Silica + (BEM + BuOH) + AcCl + TiCl.sub.4 + EADC                                                       71.1      2.87  28.6   0.9243                                                                              chunks              (4) Silica + (BEM + BuOH) + BzCl + TiCl.sub.4 + EADC                                                       12.0      0.87  33.0   Hi-density                                                                          26.0                (5) Silica + (BEM + BuOH) + BzCl + TiCl.sub.4 + EADC                                                       12.0      0.13  32.8   Hi-density                                                                          17.5                (6) Silica + (BEM + BuOH) + BzCl + TiCl.sub.4 + EADC                                                       12.0      --    --     --    21.0                (Comp. 1) Silica + BEM + TiCl.sub.4 +  EADC                                                                19.2      3.10  26.0   0.9350                                                                              20.0                (Comp. 2) Silica + (BEM + BuOH) + BzCl + TiCl.sub.4                                                        14.2      1.77  25.7   0.9379                                                                              17.5                __________________________________________________________________________

What is claimed is:
 1. A process for the polymerization of ethylene andalpha-olefins having from 1 to 20 carbon atoms or mixtures of ethylene,alpha-olefins and diolefins which process comprises polymerizing in thepresence of a catalyst system comprising (a) an organo aluminum compoundof the formula ALR"_(n) X"_(3-n) wherein R" is hydrogen or a hydrocarbylgroup having from 1 to 20 carbon atoms, X is halogen and n is a numberfrom 1 to 3, and (b) a transition metal containing catalyst componentcomprising the solid reaction product obtained by treating an inertsolid support material in an inert solvent sequentially with (A) anorganometallic compound of a Group IIa, IIb or IIIa metal wherein allthe metal valencies are satisfied with a hydrocarbon group, (B) anoxygen containing compound selected from ketones, aldehydes, alcohols ormixtures thereof, (C) an acyl halide, (D) at least one transition metalcompound of a Group IVb, Vb, VIb or VIII metal, (E) a Group IIIa metalhydrocarbyl dihalide with the proviso that the inert solid supportmaterial can alternatively be treated with (i) the (A) organometalliccompound and the (B) oxygen containing compound simultaneously, (ii) thereaction product of the (A) organometallic compound and (B) oxygencontaining compound or (iii) the (B) oxygen containing compound followedby treating with the (A) organometallic compound.
 2. The process as inclaim 1 wherein the (A) organometallic compound is a dihydrocarbonmagnesium compound represented by R¹ MgR² wherein R¹ and R² which can bethe same or different are selected from alkyl groups, aryl groups,cycloalkyl groups, aralkyl groups, alkaienyl groups or alkenyl groups,the (B) oxygen containing compounds are selected from alcohols andketones represented by the formula R³ OH and R⁴ COR⁵ wherein R³ and eachof R⁴ and R⁵ which may be the same or different can be an alkyl group,aryl group, cycloalkyl group, aralkyl group, alkadienyl group or alkenylgroup and the (C) acyl halide is represented by the formula R⁸ COXwherein R⁸ can be an alkyl group, cycloalkyl group or aryl group havingfrom 1 to 12 carbon atoms and X is halogen and the Group IIIahydrocarbyl metal dihalide is one of alkyl boron dihalide, alkylaluminum dihalide or mixtures thereof.
 3. The process as in claim 2wherein the inert solid support material is one of silica, alumina,magnesia or mixtures thereof.
 4. The process as in claim 2 wherein R¹,R², R³ , R⁴, and R⁵ are alkyl groups having from 1 to 10 carbon atoms.5. The process as in claim 2 wherein R¹ and R² are different.
 6. Theprocess as in claim 5 wherein R¹, R² and R³ are alkyl groups having from1 to 6 carbon atoms.
 7. The process as in claim 6 wherein R¹ is butyl.8. The process as in claim 7 wherein R² is ethyl.
 9. The process as inclaim 2 wherein the Group IIIa alkyl metal dihalide is one of ethylboron dichloride or ethyl aluminum dichloride.
 10. The process as inclaim 9 wherein the oxygen containing component is an alcohol havingfrom 1-4 carbon atoms.
 11. The process as in claim 10 wherein R³ isbutyl.
 12. The process as in claim 2 wherein R⁸ is an alkyl group havingfrom 1-6 carbon atoms or a phenyl group having from 7-10 carbon atomsand X is chlorine.
 13. The process as in claim 12 wherein R⁸ is methylor phenyl.
 14. The process as in claim 2 wherein the transition metalcompound or mixtures thereof is represented by the formula TrX'_(4-q)(OR⁶)_(q), TrX'_(4-q) R_(q) ⁷, VOX'₃ or VO(OR⁶)₃ wherein Tr is atransition metal, R⁶ is a hydrocarbyl group having from 1 to 20 carbonatoms, R⁷ is an alkyl group, aryl group or aralkyl group having from 1to 20 carbon atoms or a 1,3-cyclopentadienyl, X' is halogen and q is 0or a number equal to or less than
 4. 15. The process as in claim 14wherein Tr is titanium, vanadium or zirconium.
 16. The process as inclaim 15 wherein the transition metal compound is TiCl₄.
 17. The processas in claim 2 wherein the organomagnesium compound and the oxygencontaining compound are reacted together prior to contact with the inertsupport material.
 18. The process as in claim 17 wherein the oxygencontaining compound is an alkyl alcohol having from 1 to 4 carbon atomsand the magnesium containing compound is ethyl-n-butylmagnesium.
 19. Theprocess as in claim 2 wherein the R⁸ is an alkyl group having from 1 to6 carbon atoms or a phenyl group having from 7 to 10 carbon atoms and Xis chlorine.